Composition of matter and method of making



Patented Nov. 21, 1933 PATENT OFFICE COMPOSITION OF MATTER AND METHOD OF MAKING Lanni ng Parke Rankin, Dover, N. J.,

Hercules Powder Company, Wilmington,

assignor to Del., a

. corporation of Delaware No Drawing. Original application February 24,

1928, Serial No.

256,802. Dividedaml this application August 10, 1929. Serial No. 385,073

' 9 Claims. (01.134-79) My invention relates to a new composition of matter and method of producing the same. The compositionaccording .to my invention is adaptable for use, for example, as an oxidizing agent, a solvent or colloiding agent for nitrocellulose, thus making it available as an ingredient of lacquers and .to'a degree'as a drying oil.

The compositionin accordance with my invention comprises essentially a terpene alcohol,

.CmHnOH having one double bond, as for ex-,

ample, a terpineol, as alpha-terpineol, betaterpineol and the like, terpineol, or mixtures thereof, which have been ozonized or which have been ozonized and then partially decomposed by the application of heat after ozonization.

In the production of the composition in accordance with my invention, for example, commercial liquid technical terpineol comprising a mixture of isomeric terpineols, pure crystalline alpha- .terpineol, melting point 33 C. 35 C., and which when melted will remain liquid throughout ozonization, or a pine oil cut, for example, a cut boiling largely [within about the range 215 C.- 220" C. and containing about 175% alpha- ,ter'pineol, may be ozonized, for example, by pass-' ing through it oxygen or air or other gas contain g ozone, or by adding to its. liquid as, for tetrachloride containing ozone,

xample', carbon The character of the ozonized product will be affected to some extent by the method of ozonization and by the temperature of ozonization which may be effected. at a temperature. within about the range'0 .C.-80 0., though the temperature is desirably'maintained "within the more limited 'range20" C. 50 C. 1

When the desired ozonization is effected, the ozonized product is heat-treated, by the direct application of heat or by steam distillation. On heating theozonized product to say, a temperature within about the range 75 C.' 130 C. or in the case of alpha-terpineol to a temperature of say about loo-125 C. the product will decompose with formation of a product containing aldehydes, acid and ketones; the presence of the 'latter makes it an excellent solvent for nitrocellulose. In efiecting heat treatment of the ozonized product, it may be partially steam distilled.

As a more specific example of the production of the composition inaccordance with my invention from, for example, alpha-terpineol, say about two liters of crystallinealpha-terpineol, suitably melted, are ozonized with oxygen containing about 20 milligrams of ozone per liter fora period of twenty-four hours at a temperature of about 30 C. The ozonized oxygen is preferably passed into the alpha-terpineol at the rate of about two liters per minute. The ozonized product obtained will not be completely ozonized, but will be substantially more viscous than the original alpha-terpineol and will have an acid number of about 10 and a saponification number of about 70 as compared with 0 for the corresponding values of the original alpha-terpineol. The ozonized product will have an iodin liberating value, such that one gram of the ozonized product will liberate slowly more than 0.25 gram of iodin from a solu tion of potassium iodide. If desired, the period of ozonization may be prolonged beyond twenty- 1 four hours with more complete ozonization and yield of a product having increased viscosity and a higher iodin liberating value against potassium iodide solutions.

On ozonization of the terpineol, the molecule of ozone enters the terpineol molecule at the double bond in chains of three oxygen atoms, and some oxidation and polymerization'of the terpineol molecule occurs. Ozonization converts the terpineol into a strong oxidizing agent, the acid number varying from 1 to 40 and the saponification number may reach 150 or higher. The ozonized product in addition to its power as an oxidizing agent, may be of use as a drying oil and will have a colloiding effect on nitrocellulose.

When the ozonization of the terpineol, as for example, technical terpineol, is effected, the ozonized product is desirably heat-treated, as has been indicated, by the direct application of heat or by distillation with steam. The decomposition of the ozonized terpineol results in the formation of a product containing aldehydes, acids and ketones, the presence of the latter increases its solvent power on nitrocellulose. In effecting heat treatment of the ozonized product, it may be steam distilledand the decomposed product resultant from distillation or the application of heat may be given an alkali wash for the separation of acidic compounds when such are undesirable.

As an example of the production of the composition resulting from heat treatment of the ozonized product in accordance with my invention, 100 g. of the liquid terpineol of commerce may be Ozonized at a temperature of about 25 C.

for 8 hours with Ozonized oxygen containing about 20 milligrams of ozone per litre. The ozonized product is then subjected to steam distillation and about 20% distilled off as unaltered terpineol leaving a residual product which will readily colloid nitrocellulose. Where it is desired to remove acidic compounds irom the product such may be accomplished by extracting the product with, for example, a 5% solution of sodium hydroxide. The extract will on acidification yield oils boiling chiefly above 100 C. under 5 mm. Hg. pressure and a residue will be obtained consisting largely of phenols, acids, ketonic bodies and polymerized products.

The ozonized product after the heat treatment to effect partial decomposition, may be'given a second heat treatment, preferably at a temperature within about the range 90 C5130 C. in

the presence of a dehydrating agent, such as a for the purpose dilute acid, iodinor iullers earth; of converting the terpineol into hydrocarbons. This treatment gives a product having a lower boiling range, which may render it more desirable for use in lacquers. The hydrocarbons produced by dehydration may be separated by distillation leaving a highboiling product which colloids =nitrocotton and which maybeemployed as a plasticizer in lacquers. As an example or the'treatment for dehydration of the Ozonized product, say 500 cc. of alphaterpineol may be Ozonized for '10 hours at about 25 C. by passing through it 2 litres of oxygen per minute, containing 20 mg. of ozone per litre. After partial decomposition by heatingtoabout-l25 0., it may be heated with l g.'of iodin fora period of about 3 hours and at a temperature of about 120 C. Approximately of the product will be-converted into dipentene and other terpenes. On distillation on? of the terpenes, a residue will remain boiling largely about 200 C. at 25 mm. This residue will desirably colloid nitrocotton. I

The heat-treated Ozonized product, ashas been indicated, lends itself to use as a solvent or colloiding agent for nitrocellulose and may desirably be used as an ingredient of lacquers containing nitrocellulose as an ingredient. When .used asan ingredient of lacquer, the heat-treated product may replace in part other-nitrocellulose solvents and may be used in varying proportions. The following formula will beillustrative of lacquer including Ozonized heat-treated terpineol:

I Per cent Low viscosity nitrocotton Denatured alcohol. '5 Benzenenl 25 Butanol 10 Ethyl acetate 6 7 Per can! Butyl acetate 16 Gum solution 16 Diethyl phthalate 5 Ozonized and heat-treated terpineol 7 A lacquer including ozonized, heat-treated and dehydrated terpineol may be made in accordance with the following formula:

Diethyl phthalate Ozonized, heat-treated' and dehydrated terpineol 10 This application is filed as a division of the application for United States Letters Patent for Improvement in composition of matter filed by me February 24, 1928, Serial No. 256,802.

What 'I claim and desire to protect by Letters Patent is; X I

1. A lacquer including as ingredients nitrocellulose and products of a terpene alcoholhaving one double bond Which has been ozonized and'then heat treated.

2. A lacquer including as ingredients nitroe cellulose and products of aterpineolwhich has n Q Q iz d and then hea atedg,

3. A lacquer including as, ingredients flit/IQ: cellulose and productsoi alpha-terpineol which has been ozonized and th'enheat' treated.

4. A lacquer including as ingredients Li il'Qe" cellulose and the partial decomposition mode s n ozoniz unsa ura e pene' lcoho 5. 'A lacquer includin s n edien rutmcelrlulose and the partial decomposifiQKLPIQdllcts; of anozonized terpineol.

6. A lacquer including as. ingredients, nitro; cellulose and; the partial decomposition products, of an Ozonized pine oil out which distilled be.

fore ozonization largely within about. the range,

7. A lacquer inoludingas' ingredients nitr c; cellulose andproducts of alpha=terpineol which a e OB IIiZQQ and hen 1 31? trea ed to t temperature below about 130 C. A e n in s n re ients mitt-Q cellulose and products ofa terpene alcohol hay-f inc one do l on -wh h, has e n on z d and then heat treated. at. a temperature below about 130IC.

9. A lacquer including as ingredients mm.

cellulose andvproductsvof a terpineol been ozonized and then heat treated at a perature below about 130 C.

LANNINQ AR E. 

